Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G9/00—Compounds of zinc
  • C01G9/02—Oxides; Hydroxides
  • C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G15/00—Compounds of gallium, indium or thallium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/04—Compounds of zinc
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/04—Compounds of zinc
  • C09C1/043—Zinc oxide
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment

Definitions

• the invention relates to a paste containing nanoscale powder as the solid phase and a dispersant as the liquid phase.
• Pigment pastes usually consist of water and / or an organic solvent, at least one pigment, at least one binder and optionally further organic solvents, wetting agents and other additives customary for pigment pastes (cf. Volker Radke in "Pigments for Paints", Technical Academy Esslingen, Ch. 7, Dispersion of pigments, Export-Verlag, 1990 ).
• binder-free paste systems consist of water and / or an organic solvent, at least one pigment, at least one dispersant, and optionally other organic solvents, wetting agents and other additives customary for pigment pastes.
• pigment pastes are as universally applicable as possible and thus the cost-effective production of a variety sometimes quite different coatings, paints and / or paints, these pigment pastes should have the highest possible fill levels and be compatible with as many coating, paint and paint systems.
• the stated requirements generally lead to a large number of problems, such as a high viscosity of the pigment pastes, inadequate storage stability of the pigment pastes (a storage stability of the pigment pastes of at least 6 months when stored at room temperature or 1 month during storage is generally desired at 40 ° C) or poor dispersibility (ie a high specific energy input is required for dispersion or occurs Thickening of the pigment paste during the dispersing or there is a Absetzne Trent).
• problems such as a high viscosity of the pigment pastes, inadequate storage stability of the pigment pastes (a storage stability of the pigment pastes of at least 6 months when stored at room temperature or 1 month during storage is generally desired at 40 ° C) or poor dispersibility (ie a high specific energy input is required for dispersion or occurs Thickening of the pigment paste during the dispersing or there is a Absetzne Trent).
• pigment pastes according to the prior art contain either water or organic solvents in order to keep the viscosity of the pigment pastes as low as possible and yet to achieve high degrees of filling.
• water In reactive, two-component isocyanate-crosslinking paint systems, water often leads to undesirable side reactions, such as bubble or foam formation.
• volatile compounds are only partially suitable as solvents for paste systems, since they pollute the environment by odors and / or volatile solvent components (VOC "volatile organic compounds") and involve the risk of the formation of explosive gas mixtures.
• paste systems which exhibit further improved properties over the prior art.
• properties of the paste for example when incorporating the paste in a paint system to be obtained.
• the paste should be such that the burden on the environment by volatile organic compounds (VOC) is reduced or avoided altogether, that it has high filling levels and a sufficient storage stability.
• VOC volatile organic compounds
• paste is to be understood as meaning a solid / liquid system which contains at least one nanoscale powder and at least one dispersant but no solvent or only in such amounts that the VOC content of the paste is less than 1% by weight. is.
• Dispersants are understood to mean agents which facilitate the dispersion of particles in a dispersion medium, the liquid phase of a dispersion, by lowering the interfacial tension.
• the property of the dispersant, by reducing the interfacial tension between the solid and liquid phases, to facilitate dispersion of the particles is manifested when the paste of the invention is dispersed in a subsequent step with an aqueous or organic liquid.
• the dispersants assist in breaking up agglomerates, as surfactants, they wet the surface of the particles to be dispersed and stabilize them against undesired reagglomeration.
• dispersion means a solid / liquid system in which the solid phase contains a nanoscale powder and the liquid phase contains at least one dispersant and at least one solvent.
• the VOC content of the dispersion may be greater or less than 1 wt .-%.
• the solvent may be water, a polar and / or a nonpolar, organic solvent.
• volatile organic compound any organic compound having a vapor pressure of 0.01 kPa or more at 293.15K.
• organic compound any compound containing at least the element carbon and further hydrogen, halogens, oxygen, sulfur, phosphorus, silicon or nitrogen other than carbon dioxide and inorganic carbonates and bicarbonates.
• nano-scale means powders having an average aggregate or agglomerate size ⁇ 1000 nm and / or a primary particle size ⁇ 100 nm.
• equilibration is meant the distribution of the particle-bound water between the solid and the liquid phase of the paste according to the invention.
• the VOC content of the liquid phase may preferably be less than 1 g / l.
• liquid phase of the paste according to the invention has a water content of less than 0.1% by weight.
• the nanoscale powder of the paste according to the invention contains a maximum of up to 3 wt .-%, particle-bound water according to the equilibrium.
• the proportion of the nanoscale powder, based on the total amount of the paste, is preferably 60 to 90 wt .-% and particularly preferably 75 to 85 wt .-%.
• the nanoscale powder is largely evenly distributed in the paste. If the contents of nanoscale powder are determined at different points of a paste, the values found usually do not differ more than ⁇ 5% from the mean value. Advantageously, the values do not differ more than ⁇ 1%, with a range of ⁇ 0.1% being particularly preferred.
• the average diameter of the nanoscale particles in the paste according to the invention may preferably be less than 300 nm and more preferably less than 200 nm.
• nanoscale powder present in the paste according to the invention is not limited.
• nanoscale powder in the form of a metal, a metal oxide, a metal boride, a metal carbide, a metal carbonate, a metal nitride, a metal phosphate, a Metal chalcogenides, a metal sulfate and / or a metal halide are present.
• the metal may preferably be Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Te, Se, Tl, Si, Ge, Sn, Pb, P, As, Sb and / or Bi.
• the non-metals B, Si, and P should also be included.
• a metal oxide containing the elements Si, Al, Ti, Fe, Ce, In, Sb, Sn, Zn, Y and / or Zr may be preferred. It may be particularly advantageous if the paste of the invention metal mixed oxides such as indium tin oxide, antimony tin oxide, mixed oxides with matrix domain structure such as those in EP-A-1284485 or in EP-A-1468962 described, included.
• the paste of the invention may also be a by precipitation, such as in WO00 / 14017 described containing metal oxide produced.
• the paste according to the invention may further contain surface-modified nanoscale powders, in particular metal oxides.
• the surface modification includes adsorption, surface reactions or complexation of or with inorganic and / or organic reagents.
• the paste according to the invention may, for example, contain a nanoscale cerium oxide powder whose surface carries carbonate groups. Such a powder is in the German patent application with the application number 10 2005 038 136.7 and 12.08.2005 disclosed as the filing date.
• Surface modification also includes the adsorption of bioorganic materials, such as nucleic acids or polysaccharides.
• the paste according to the invention also contains at least one dispersant.
• R " H.
• R ' is usually derived from an alcohol R'OH which acts as a starting alcohol for the polymerization of the styrene oxide and alkylene oxide.
• R'OH an alcohol
• R'OH an alcohol
• R'OH an alcohol
• R'OH an alcohol
• R'OH an alcohol
• R'OH an alcohol
• R'OH an alcohol
• R'OH an alcohol
• R'OH an alcohol
• R'OH methyl, butyl, stearyl, allyl Hexenyl, nonylphenyl or oleyl radical.
• Preferred for R ' are methyl and butyl radicals.
• Such dispersants are for example in EP-A-940 406 described.
• terminal OH groups may also be anionically modified, for example sulfated, sulfonated, phosphorylated (see general formula 2 ) or also carboxy-modified.
• the reaction products may be in the form of the amides and / or the corresponding salts. If the molecule part "Z" has a multiple bond, as may be the case, for example, in the case of the polyethers and the alcohol-initiated polyesters in which the terminal OH group has been esterified with an unsaturated acid, such as (meth) acrylic acid, the bond takes place via a Michael addition of the NH function to the double bond.
• an unsaturated acid such as (meth) acrylic acid
• amino-functional polymers are amino-functional polyamino acids such as polylysine from Aldrich Chemical Co .; amino-functional silicones which are sold under the trade name Tegomer® ASi 2122 by Degussa AG; Polyamidoamines sold under the tradename Polypox®, Aradur® or "Starburst®” Dendrimers by Aldrich Chemical Co .; Polyallylamines and poly (N-alkyl) allylamines which are available under the trade names PAA from Nitto Boseki; Polyvinylamines, which are sold under the trade name Lupamin® by BASF AG; Polyalkyleneimines such as polyethyleneimines sold under the trade names Epomin® (Nippon Shokubai Co., Ltd.), Lupasol® (BASF AG); Polypropyleneimines available under the trade name Astramol® from DSM AG.
• amino-functional polyamino acids such as polylysine from Aldrich Chemical Co .
• amino-functional silicones which are
• amino-functional polymers are the o.g. Systems by crosslinking with amine-reactive groups. This crosslinking reaction takes place for example via polyfunctional isocyanates, carboxylic acids, (meth) acrylates and epoxides.
• poly (meth) acrylate polymers which include dimethylaminopropyl (meth) acrylamide (Degussa AG) or dimethylaminoethyl (meth) acrylate (Degussa AG) as monomers.
• amino-functional polymers having a molecular weight of from 400 g / mol to 600,000 g / mol are used.
• radical T examples include alkyl radicals having 1 to 24 carbon atoms, such as the methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, tert-butyl, hexyl, iso-hexyl, octyl , Nonyl, iso-nonyl, decyl, dodecyl, hexadecyl and octadecyl.
• optionally substituted Aryl or arylalkyl radicals having up to 24 carbon atoms are the phenyl, benzyl, toluyl or phenethyl radical.
• a particularly preferred embodiment of the present invention is characterized in that the polyester group by per se known methods by ring-opening polymerization with a starter molecule such as T-CH 2 -OH or T-COOH and one or more lactones, such as ⁇ -propiolactone, ⁇ Butyrolactone, ⁇ -butyrolactone, 3,6-dimethyl-1,4-dioxane-2,5-dione, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, 4-methylcaprolactone, 2-methylcaprolactone, 5 Hydroxydodecanoic acid lactone, 12-hydroxydodecanoic acid lactone, 12-hydroxy-9-octadecenoic acid, 12-hydroxyoctadecanoic acid.
• a starter molecule such as T-CH 2 -OH or T-COOH
• lactones such as ⁇ -propiolactone, ⁇ Butyrolactone, ⁇
• Starter molecules such as T-COOH - and the fatty alcohols T-CH 2 -OH which can be prepared therefrom are preferably monobasic fatty acids based on natural vegetable or animal fats and oils having 6 to 24 carbon atoms, in particular having 12 to 18 carbon atoms and known in this field such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, oleic acid, linoleic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, tall oil fatty acid which alone or in a mixture in the form their glycerides, methyl or ethyl esters or can be used as free acids, as well as incurred in the pressure splitting technical mixtures.
• the iodine number is the amount of iodine absorbed by 100 g of the compound to saturate the double bonds.
• Both the fatty acids and the resulting alcohols can be modified by addition of alkylene oxides, in particular ethylene oxide and / or styrene oxide.
• Examples of the polyether building blocks of B are alkylene oxides such as: ethylene oxide, propylene oxide, butylene oxide, styrene oxide, dodecene oxide, tetradecene oxide, 2,3-dimethyloxirane, cyclopentene oxide, 1,2-epoxypentane, 2-isopropyloxirane, glycidylmethyl ester, glycidyl isopropyl ester, epichlorohydrin, 3-methoxy 2,2-dimethyloxirane, 8-oxabicyclo [5.1.0] octane, 2-pentyloxirane, 2-methyl-3-phenyloxirane, 2,3-epoxypropylbenzene, 2- (4-fluorophenyl) oxirane, tetrahydrofuran, and their pure enantiomeric pairs or enantiomers.
• alkylene oxides such as: ethylene oxide, propylene oxide, butylene oxide, s
• the group Z may be selected from addition products of the carboxylic acid anhydrides, e.g. Succinic anhydride, maleic anhydride or phthalic anhydride.
• the ratio by weight of polyester to polyether in the dispersing resin according to the invention is between 50: 1 and 1: 9, preferably between 40: 1 and 1: 5 and particularly preferably between 30: 1 and 1: 1.
• R 3 may be hydrogen.
• R 4 may be hydrogen or an acrylic radical.
• Such dispersants are for example in EP-A-1382632 described.
• Such dispersants are for example in DE-A-10348825 described.
• the paste of the invention may preferably consist of a solid phase of at least one nanoscale powder and a liquid phase of at least one Dipsergierstoff.
• a paste according to the invention may be preferred in which the solid phase consists of a nanoscale powder and the liquid phase consists of a dispersant.
• Another object of the invention is a method for producing the paste according to the invention in which the nanoscale powder is incorporated all at once, continuously or in portions under dispersing conditions in the liquid phase.
• the dispersion can be carried out, for example, with a mortar, roller mill, ball mill, rotor-stator, Planetary kneaders or with other known to the expert dispersing done.
• a further subject of the invention is a dispersion obtainable from the paste according to the invention and a solvent.
• the solvent may be water, one or more polar, organic solvents, and / or one or more nonpolar organic solvents.
• the content of nanoscale powder is preferably from 0.5 to 50% by weight, based on the dispersion.
• Another object of the invention is a process for the preparation of the dispersion according to the invention in which the paste is mixed by stirring or by shaking with a solvent or solvent mixture.
• Another object of the invention is the use of the paste according to the invention for the production of paints, (printing) paints, coatings, adhesives and moldings.
• the VOC content is determined according to DIN EN ISO 11890-1.
• the calculation of the VOC content is less water according to procedure 8.4.
• the water content is determined titrimetrically according to Karl Fischer (ISO 760).
• the particle size determination takes place by means of dynamic light scattering in a 1 percent dispersion.
• the dispersion is carried out by stirring, shaking or ultrasound.
• the particle size analyzer used is the HORIBA LB-500.
• temperature, viscosity and refractive index of particles and dispersion medium must be known.
• Solid content determination of the paste Approximately 0.2 - 0.3 g of the paste is weighed into a tared glass. The exact weight of the sample with glass is noted and the glass is annealed with the paste for 1 hour at 400 ° C in the Carbolite oven. After cooling of the glass with the paste remainder this is again balanced. The weight is divided by the weight and taken 100 times, you get the solids content of the paste in percent. For determination, the content of various sites of a paste is determined.
• Zinc oxide (according to WO2005 / 028565 Zinc powder (510 g / h) is transferred by means of a stream of nitrogen (4.2 Nm 3 / h) in a reductive evaporation zone, where a hydrogen / air flame (hydrogen: 4.0 Nm 3 / h, air: 8.0 Nm 3 / h) burns.
• the zinc powder is evaporated.
• the reaction mixture of zinc vapor, hydrogen, nitrogen and water flows into the oxidation zone in which 20 Nm 3 / h of air is added.
• the temperature before addition of the oxidation air is 956 ° C.
• the temperature before adding the quenching air is 648 ° C.
• the resulting zinc oxide powder is separated by filtration from the gas stream.
• the BET surface area of the zinc oxide powder is 27 m 2 / g.
• Indium tin oxide according to WO00 / 14017 140 g of indium (+ III) chloride (0.63 mol anhydrous), 18 g of tin (+ IV) chloride x 5 H2O and 5.6 g of caprolactam are added to 1400 ml of water and stirred. After a clear solution has formed, it is heated to 50 ° C and then added dropwise 105 ml of 25 percent ammonium hydroxide solution. The dispersion is stirred at a temperature of 50 ° C for 24 hours. Then another 280 ml of ammonium hydroxide solution are added. The white precipitate is removed by centrifugation in a vacuum oven at 190 ° C until dried a slight yellowing of the powder is noted.
• the dried precipitate is finely ground and placed in a forming gas oven.
• the furnace is evacuated, then flooded with nitrogen.
• the furnace is heated at a heating rate of 250 ° C / hour to 250 ° C at a nitrogen flow of 200 liters / hour. This temperature is maintained for 60 minutes under a forming gas atmosphere at a gas flow of 300 liters / hour. Thereafter, the oven cools down to room temperature under a nitrogen atmosphere (duration: about 5 hours). This results in a dark blue powder.
• the indium tin oxide powder thus produced is used in Examples ITO-1 to ITO-12.
• Indium tin oxide according to DE-A-10311645 : An aqueous solution containing 88.9 g / l indium (III) chloride and 8.4 g / l tin (IV) chloride are by means of compressed air and a nozzle (diameter 0.8 mm) with a flow rate of 1500 ml / h in the reaction tube atomized.
• a blast gas flame burns out 5 m 3 / h hydrogen and 15 m 3 / h air.
• the temperature 0.5 m below the flame is 750 ° C.
• 2.5 m below the flame are fed 10 m 3 / h forming gas, the temperature is above the addition point about 450 ° C.
• the reaction mixture passes through a residence time of 2 m length in 14 sec .. Then the solid is separated by means of a filter from the gaseous substances and treated over a period of 15 minutes at a temperature of 250 ° C with continuous supply of forming gas.
• the ratio In 2 O 3 / SnO 2 is 94/6, the BET surface area is 53 m 2 / g.
• the indium tin oxide powder thus produced is used in Examples ITO-13 and ITO-14.
• dispersants are used: LA-D 1045, Dispers 650, Twin 4000, Dispers 650-carboxy, Dispers 655, LA-D 868, LA-D 869. All TEGO, all VOC ⁇ 10 g / l.
• the paste of the invention is mixed with a solvent by stirring with a magnetic stirrer (10 min at the highest stage), by shaking or by ultrasound.
• Example ITO-2 With the paste according to the invention from Example ITO-2, a dispersion with water, polar and non-polar organic solvents can be prepared.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Colloid Chemistry (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Conductive Materials (AREA)
• Paints Or Removers (AREA)

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• 2005
  • 2005-08-25 DE DE102005040157A patent/DE102005040157A1/de not_active Withdrawn
• 2006
  • 2006-08-01 EP EP06118230A patent/EP1757664A3/fr not_active Withdrawn
  • 2006-08-22 JP JP2006225626A patent/JP2007056264A/ja active Pending
  • 2006-08-24 CN CNB2006101212864A patent/CN100484998C/zh not_active Expired - Fee Related
  • 2006-08-25 US US11/509,741 patent/US20070199477A1/en not_active Abandoned

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